Substituted v-triazolyl-2-stilbenes and their use for brightening materials



United States Patent cc 3,453,268

Patented July 1, 1969 3 453 268 materials, such as cotton and paper, or of wool, furthermore for the brightening of synthetic materials, such as fibres, filaments, films or plastic masses of polyamides,

Alfons Dorlars and Otto Neuner, Leverkusen, and Rolf polyesters, polyacrylonitrile, polyvinyl chloride and celluputter, D Id -f Germany, assignm-s to p 5 lose acetates and also for the brightening of lacquers fabriken Bayer Aktiengesellschaft, Leverkusen, Ger- C isting of cellulose acetates, brightening P- many, a corporation of Germany For the brightening of cotton and synthetic polyamides, N0 Drawing. Filed Jan. 5, 1967, Ser. No. 607,391 preferably those v-triazolyl-(2)sti1bene compounds are Claims pg zgii gpp g s i g gg g gz 1966, suitable which correspond to the Formula I when Y r i e stands for an optionally substituted v-triazolyl-(Z) or r US. Cl. 2223525 23/14 55/00 C07! 55/024 Claims pyrazolyl-(1) radical and X and X denote the sulphonic acid group, while those compounds which correspond to the Formula I but are free from sulphonic acid groups are mainly suitable for the brightening of materials con- ABSTRACT OF THE ISC sisting of polyesters, polyvinyl chloride and cellulose ace- An aryl substituted v-triazolyl-Z-stilbene and use as iaies and for brightening lacquers c0nsisiing of Cellulose brightening agents when applied to polyesters, polyvinyl aceiateschloride, cellulose acetate or lacquers based on cellulose The brightening agents y e used 111 nventlonal t manner, e.g., 1n the form of aqueous solutions or dispersions or in the form of solutions in organic solvents,

such as ethyleneglycol monomethyl ether, dimethylform- The present invention particularly relates to brightenamide and tiiethanoiaminff- If i the brightening ing agents consisting essentially of blue-fluorescent v-triagents may also be usfid in comiiliiatlon w Washing azolyl z stilbene compounds f the f l agents or added to casting compositions which serve for N the preparation of films or filaments. Brightening agents R1 which contain carboxylic acid groups, carboxylic acid N- -orr=on y ester groups or carboxylic acid amide groups may also I I be used in the preparation of fluorescent shaped articles N I of synthetic polycondensates according to the process of the British patent specification No. 827,745. The necessary amounts can easily be determined in each case by preliminary experiments; in general, amounts of 0.1 to 1% by weight, referred to the material to be brightened, have proved sutficient.

Symmetrical brightening agents which correspond to the Formula I when R stands for an acylated amino group, halogen or cyano and R has the meaning stated above can be obtained, for example, by condensing bishydrazinostilbene compounds of the formula wherein R stands for halogen, cyano, an acylated amino group, the carboxylic acid group, a carboxylic acid ester group or an optionally substituted carboxylic acid amide group, and R stands for an optionally substituted aryl radical, while X and X independently of each other, denote hydrogen, the sulphonic acid group, a sulphonic acid ester group, an optionally substituted sulphonic acid amide group, an alkylsulphone or arylsulphone group, the carboxylic acid group, a carboxylic acid ester group, an optionally substituted carboxylic acid amide group or cyano, and Y stands for hydrogen, halogen, an acylated amino group, an optionally substituted v-triazolyl group HiN NH CH=CH NH NH or an optionally substituted pyrazolyl group. &

As substituents of the carboxylic acid amide groups i H and sulphonic acid amide groups for which the symbols wherein X and X have the same meaning as above 1 and 1 and 2 y Stand, alkyl and y radicals are with 1,2,4-oxadiazoles of the formula mentioned; as aryl radical R above, all the phenyl and the naphthyl radicals are elgible and as substituents for lkfi fi these there are mentioned, for example, halogen, cyano o N (3-H;

and alkyl, alkoxy, acylamino, sulphonic acid, sulphon- 0 HI amide, alkylsulphone and arylsulphone groups. As substituents of the v-triazolyl and pyrazolyl groups for which wherein R has the same meaning as the above and R the symbol Y may stand, alkyl groups and the substituents stands for an optionally substituted alkyl or aryl radical, for which the symbols R and R may stand are eligible; for instance, with 3-benzoyl-5-methyl-1,2,4-oxadiazole,

the v-triazolyl groups for which the symbol Y may stand 3-toluyl-5-methyl-1,2,4-oxadiazole or S-benzoyl-S-phenylcan also be benzotriazolyl and naphthotriazolyl groups 1,2,4-oxadiazo1e and converting the resultant bis-hydrawhich may be substituted by alkyl, alkoxy and/or sulzones into the bis-[v-triazolyl-(Z)]-stilbene compounds phonic acid groups. of the formula The brightening agents of the present invention are whereupon the two acylated amino groups R .CO.NH

suitable as such or in the form of their salts, particularly may be hydrolyzed to form the free amino groups which in the form of their alkali metal salts or in the form of are then combined with a diiferent acyl radical or ditheir salts with amines, for the brightening of a great azotized and replaced by halogen or cyano according to variety of materials, for example for brightening cellulose Sandmeyer.

These symmetrical brightening agents can also be obtained by coupling diazo compounds of diaminostilbene compounds of the formula wherein X and X have the meaning stated above with u-nitroketoximes of the formula OzN-CH:

for instance, with w-nitroacetophenoneoxime, converting the resultant disazo compounds into the corresponding bis-nitrotriazolyl-(Z)-stilbene compounds and reducing the nitro groups to amino groups whereupon the amino groups are acylated or diazotized and replaced by halogen or cyanogen according to Sandmeyer.

Symmetrical brightening agents which correspond to the Formula I when R stands for cyano, the carboxylic acid group, an optionally substituted carboxylic acid amide group and R has the meaning stated above are obtainable for example by coupling diazo compounds of diaminostilbene compounds of the Formula V with appropriate enamines of the formula wherein R has the meaning stated above and R stands for cyano, the carboxylic acid group, a carboxylic acid ester group or an optionally substituted carboxylic acid amide group, or with their tautomeric ketimides, for instance with ,B-aminocinnamic acid nitrile, fl-aminocinnamic acid methyl or ethyl ester, or fl-aminocinnamic acid amide, converting the resultant disazo compounds into the copper complexes, transforming these into the bis-[v-triazolyl-(2)-stilbene compounds by heating and, if desired, hydrolysing the cyano, carboxylic acid ester or carboxylic acid amide group to the carboxylic acid group.

S O Na.

Unsymmetrical brightening agents of the Formula I can for example be obtained by converting monohydrazino stilbene compounds of the formula CH=OH N02 X1 X1 VIII or diazo compounds of monoaminostilbene compounds h l oft e formu a N CH=CH -NO1 R2 N X1 X: x

reducing the nitro group into the amino group and converting the amino group in known manner into the substituent Y of the meaning given at the beginning.

Unsymmetrical brightening agents which correspond to the Formula I when Y stands for hydrogen, halogen, or an optionally substituted v-triazolyl or pyrazolyl group can also be prepared by converting the hydrazino group of monohydrazinostilbene compounds of the formula or the diazotized amino group of diazo compounds of monoaminostilbene compounds of the formula wherein X and X have the meaning stated above and Y stands for hydrogen, halogen or an optionally substituted v-triazolyl or pyrazolyl group with the aid of 1,2,4- oxadiazoles of the Formula III, a-nitroketoximes of the Formula VI or of enamines of the Formula VII or their tautomeric ketimides into the grouping R C=N N. R2-C=N in the manner described above for the production of the symmetrically built brightening agents.

The brightening effects obtained by the agents of the present invention are surprisingly fast to light and chlorine.

The following examples serve to illustrate the invention without, however, limiting its scope.

EXAMPLE 1 Cotton fabric is moved for 30 minutes at 40-50 C. in a liquor ratio of 1:20 in an aqueous bath which contains, per litre, 0.06 g. of the brightening agent of the formula N=C-COOII The fabric is then washed and dried. It shows a clear, neutral brightening which possesses very good fastness to light and chlorine.

. The brightening agent used was prepared in the followmg manner:

A diazo suspension obtained in the usual manner by diazotisation of 37 g. 4,4 diaminostilbene 2,2 disulphonic acid was added at 10 C., with stirring, to a solution of 40 g. B-aminocinnamic acid ethyl ester in 800 ml. alcohol, the reaction of the coupling mixture constantly being kept mildly acetic acid by adding concentrated aqueous sodium acetate solution. After coupling was ended the disazo compound formed Was filtered off with suction, dissolved in 2 liters of 60% alcohol, and a solution of g. crystallised copper-II-sulphate in a mixture of 150 ml. of Water and ml. concentrated aqueous ammonia was added. The reaction mixture was then heated for 3 hours on a water bath, the alcohol being gradually distilled off under reduced pressure. After the mixture was cold and sodium chloride solution had been added to it, the precipitated reaction product Was filtered off with suction and boiled out with hot, dilute sodium hydroxide solution. The alkaline extracts were filtered and sodium chloride was added to them. The precipitated product was filtered off and purified by repeated recrystallisation from water to which a little sodium hydroxide solution and sodium dithionite had been added. After this the product was dissolved in hot water, the solution was acidified with acetic acid and sodium chloride was NaOaS added to it, and the precipitate formed was filtered off and dried. The brightening agent so obtained is a pale yellow powder which dissolves in water with blue fluorescence.

Similar brightening effects are obtained when instead of the brightening agent described above the same amount of a compound of the formula 6 wherein R stands for OH, or C(CH These brightening agents were prepared in the following manner:

A diazo suspension obtained in the usual manner by diazotization of 37 g. 4,4-diaminostilbene-2,2'-disulphonic acid was added at C., with stirring, to a solution of 40 g. w-nitroacetophenoneoxime in 500 ml. ethyl alcohol,

wherein Z stands for CH OCH or Cl is used. These brightening agents were prepared by applying 43 g. of

methoxyphenyl)-acrylic acid ethyl ester or S-amino-B-(pchlorophenyl)-acrylic acid ethyl ester instead of 40 g. of fi-athinocinnamic acid ethyl ester in the process described above.

EXAMPLE 2 Unbleached cotton yarn is treated at 85 to 95 C. for one hour in a liquor ratio 1:20 in an aqueous bath which contains, per liter, 2 g. sodium chlorite and 0.06 g. of one of the brightening agents mentioned in Example 1. After washing and drying, the treated yarn shows a clear brightenirig of good fastness to light.

EXAMPLE 3 White washing is washed for minutes at 90 to 100 C. in a liquor ratio 1:20 in a wash liquor which contains, per litre, 10 g. of a commercial anion-active washing agent and 0.05 g. of one of the brightening agents mentioned in Example 1. After washing and drying, the washed material shows an outstanding brightening of very good fast'ness to light.

I EXAMPLE 4 Fabrics consisting of fibres which were prepared from poly-e-caprolactam are moved for 30 minutes at 80-90 C. in a liquor ratio 1:40 in an aqueous bath which con- 45 tains, per liter, 2 g. sodium chlorite and 0.2 g. of one of the brightening agents mentioned in Example 1 or of the brightening agent of the formula SO Na NaOaS After washing and drying, the fabrics show a clear brightening of very good fastness to light.

The brightening agent of the above formula was prethe pH-value of the reaction mixture being adjusted to about 5 by the addition of sodium acetate. After coupling was ended ml. concentrated aqueous sodium chloride solution was added with stirring. The disazo compound formed was filtered oif with suction, dried in a vacuum and pulverized. The resulting oximino-nitrohydrazone which contained sodium chloride was suspended with 40 g. anhydrous sodium acetate in 800 ml. acetic anhydride at room temperature. The suspension was mixed with 250 ml. dimethylformamide and stirred for 6 hours while the 0 temperature was raised gradually to C. After the acetic acid and the main portion of the excess acetic anhydride had been distilled ofl at reduced pressure, the residue was stirred in water and filtered off with suction. The crude nitrotriazole thus obtained was purified by recrystallization from isopropanol/Water, then dissolved in 400 ml. dimethylformamide and reduced with hydrogen to the aminotriazole compound at a maximum temperature of 50 C. in the presence of Raney nickel catalyst. The catalyst was filtered off and the filtrate was concentrated in a vacuum. The aminotriazole compound which precipitated in the form of yellow crystals was filtered off with suction, washed with cold methanol and dried. It was then acylated in pyridine with acetic anhydride or pivalolyl chloride respectively. Finally the brightening agents thus obtained were recrystallized from aqueous ethanol.

EXAMPLE 5 A fabric consisting of filaments which were prepared from hexamethylene-adipic acid polymer is moved for 30 minutes at 80 to C. in a liquor ratio 1:40 in an aqueous bath which contains, per liter, 0.2 g. of one of the brightening agents mentioned in Example 1. After washing and drying, the fabric thus treated shows a strong, clear brightening, which possesses very good fastness to light and chlorite.

Similarly good results are achieved when, instead of R is phenyl, naphthyl or the corresponding substituted the brightening agents mentioned in Examle 1, the same radicals having as substituents a member selected amount of the compound of the formula from the group consisting of halo, cyano, alkyl, alki d, oxy, acylamino, sulfonic acid, sulfonamido, alkyl- This brightening agent was prepared by following the sulfone and arylsulfone; method described in Example 1 but applying 39 g. X and X are independently defined as a hydrogen, B-amino-fi-(p-tolyl)-acrylic acid amide instead of 40 g. sulfonic acid, the corresponding alkali metal or B-aminocinnamic acid ethyl ester. It is a pale yellow amine salt of sulfonic acid, sulfonic acid ester, sulpowder which dissolves in water with blue fluorescence. fonic acid amide, alkyl-sulfone, phenyl-sulfone, car- EXAMPLE 6 lgggylaigdacid, carboxylic acid ester, carbamyl or cy- A mixture of 900 g. e-caprolactam, 190 g. w-arnino- Y is defined as hydrogen; halo; benzotriazolyl; naphthocaproic acid, 0.5 g. acetic acid, 13.5 g. t1tan1um d10Xlde triazolyl; the corresponding substituted rings having and 4 g. of one of the brightening agents mentlonfid m as substituents members selected from the group con- Example 1, in the first paragraph of mp e 4 Or 111 h sisting of alkyl, alkoxy, and sulfonic acid groups; vsecond paragraph of Example 5 are heated to 260 C- 1 n triazolyl-(Z); and v-triazolyl-(Z) having as substituents a stainless steel container for 5 hours at atmospherlc a member selected from the group consisting of R pressure. The polyamide melt which is formed is processed d into chips in known manner and the chips are then spun 3, Acompound f th f l into filaments with a final titre of 290/ 25 The light-fastness and the fastnesses to wetting of the brightening achieved RI are outstanding. N-ClI=CH-Y We claim: R2

\N la 1. A compound of the formula R wherein N --CH=CH Y R is carboxy, carbamyl and lower alkanoylamino; R2 R is phenyl, lower alkyl phenyl, lower alkoxyphenyl or N X, X2 chlorophenyl;

X and X are SO Na; and wherein Y is a 1,2,3,-v-triazolyl radical having as substituents R andR R 1s carboxy; 40 1 z R2 fi z lqwer alkyl phenyl lower alkoxyphenyl or :1 :1 e i la i izi d ffioi n ihi group consisting of c orop eny X1 and X2 are SO3Na, gleeitlagndo and tertiary butyl carbonyl- Y is a 4-carboxy-1,2,3-v-tr1azolyl radical having as the R h 1 th 1 m h S-substituent a member selected from the group con- 3 li f c P y fi of g fi alkyl phenyl lower alkoxy- Y iz a me mlfer sele teiffrom the group consisting of 4 en an c are any A c 2 ound of f formula carbamyl-5-phenyl-v-tr1azolyl-(2)-4-lower alkyl carbonyl amino, 5-phenyl-v-triazolyl-(2), and 4-carbarnyl-S-methylphenyl-v-triazolyl- (2) N -orr=on Y References Cited m UNITED STATES PATENTS 2,901,476 8/1959 Gold m1. wherein JOHN D. RANDOLPH, Primary Examiner. R 15 a halo, cyano, lower alkanoylamino, benzoylamino,

methyl benzoylamino, carboxylic acid, carboxylic 1 acid alkyl ester having 14 carbon atoms in the alkyl group or carbamyl; 106-176, 117-335, 252-117, 301.2, 26037 

